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DOE OSTI · 1534573

Linear-Response Time-Dependent Embedded Mean-Field Theory

Ding, Feizhi·Tsuchiya, Takashi·Manby, Frederick R.·Miller, Thomas F.
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Abstract

We present a time-dependent (TD) linear-response description of excited electronic states within the framework of embedded mean-field theory (EMFT). TD-EMFT allows for subsystems to be described at different mean-field levels of theory, enabling straightforward treatment of excited states and transition properties. We provide benchmark demonstrations of TD-EMFT for both local and nonlocal excitations in organic molecules, as well as applications to chlorophyll a, solvatochromic shifts of a dye in solution, and sulfur K-edge X-ray absorption spectroscopy (XAS). It is found that mixed-basis implementations of TD-EMFT lead to substantial errors in terms of transition properties; however, as previously found for ground-state EMFT, these errors are largely eliminated with the use of Fock-matrix corrections. These results indicate that TD-EMFT is a promising method for the efficient, multilevel description of excited-state electronic structure and dynamics in complex systems.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYembeddingenergyoscillationtime dependant density functional theory

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Ding, Feizhi, Tsuchiya, Takashi, Manby, Frederick R., Miller, Thomas F.. 2017-08-11. Linear-Response Time-Dependent Embedded Mean-Field Theory. https://doi.org/10.1021/acs.jctc.7b00666

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